Bioavailability Of Polycyclic Aromatic Hydrocarbons Research Articles

State of polycyclic aromatic hydrocarbon (PAH) contamination in the Saint John Harbour, New Brunswick, Canada

This study examined the concentrations and compositions of polycyclic aromatic hydrocarbon (PAH) contaminants in the surficial sediments of the Saint John Harbour (SJH) and assessed PAH exposure to local aquatic biota. Our findings suggest that sedimentary PAH contamination is heterogeneous and widespread in the SJH, with several sites exceeding the Canadian and NOAA recommended guidelines for the protection of aquatic life. Despite high concentrations of PAHs at some sites, there was no indication that local nekton was affected. Lack of a biological response may be due in part to a low bioavailability of sedimentary PAHs, presence of confounding factors (e.g., trace metals), and/or adaptation of local wildlife to the historic PAH contamination in this region. Overall, although no indication of effects to wildlife was observed with the data collected in the present study, continued efforts should be made to remediate highly contaminated areas and reduce the prevalence of these compounds.

Effects of biodegradable and non-biodegradable microplastics on bacterial community and PAHs natural attenuation in agricultural soils

Anthropogenic activities such as in situ straw incineration and the widespread use of agricultural film led to the accumulation of polycyclic aromatic hydrocarbons (PAHs) and microplastics (MPs) in agricultural soils. In this study, four biodegradable MPs (BPs), including polylactic acid (PLA), polybutylene succinate (PBS), poly-β-hydroxybutyric acid (PHB) and poly (butylene adipate-co-terephthalate) (PBAT) and non-biodegradable low-density polyethylene (LDPE) were selected as representative MPs. The soil microcosm incubation experiment was conducted to analyze MPs effects on PAHs decay. MPs did not influence PAHs decay significantly on day 15 but showed different effects on day 30. BPs reduced PAHs decay rate from 82.4% to 75.0%− 80.2% with the order of PLA < PHB < PBS < PBAT while LDPE increased it to 87.2%. MPs altered beta diversity and impacted the functions to different extents, interfering in PAHs biodegradation. The abundance of most PAHs-degrading genes was increased by LDPE and decreased by BPs. Meanwhile, PAHs speciation was influenced with bioavailable fraction elevated by LDPE, PLA and PBAT. The facilitating effect of LDPE on 30-d PAHs decay can be attributed to the enhancement of PAHs-degrading genes and PAHs bioavailability, while the inhibitory effects of BPs were mainly due to the response of the soil bacterial community.

Novel insights into the predominant factors affecting the bioavailability of polycyclic aromatic hydrocarbons in industrial contaminated areas using PLS-developed model

Bioavailability is recognized as a useful technical standard for risk assessment and pollution rehabilitation. However, knowledge on the bioavailability of polycyclic aromatic hydrocarbons (PAHs) in contaminated site soils is still limited, especially concerning the influential mechanism. With an abundance of soil collections from nine industrial areas in China, the bioavailabilities, as conceptually defined as bioconcentration factors (BCFs) of PAHs were analyzed using biomimetic extraction of hydroxypropyl-β-cyclodextrin (HPCD). Apart from the total content of PAHs varying with the different pyrogenic sources, the BCFs were greatly dependent on the soil physicochemical properties from the spatial scale and inversely proportional to the number of rings. Pearson correlation analysis indicated a weak relationship between bioavailability and the soil dissolved organic matter (DOM), pH and particle size. To incorporate the soil physicochemical properties and structural characteristics of PAHs determined by density functional theory (DFT), the optimum model for bioavailability was developed for BCFs by partial least square (PLS) analysis. The PLS-derived model was shown to be predictive within the applicability domain (AD). The structural characteristics, e.g., molecular polarizability and frontier orbital energy level that favor the soil adsorption of PAH isomers via dispersion interactions, and electron exchanges were indicated to be more impactful on bioavailability than soil environmental factors. However, soil factors should not be neglected, because the pH, DOM, etc. were significantly influential. It makes sense that the higher DOM causes greater bioavailability via increasing the free-dissolved fractions of PAHs. Interestingly, the effect of pH on bioavailability was spectrally validated by excitation-emission matrix (EEM) fluorescence, showing that the interaction between DOM and pyrene strengthened the fluorescence quenching of chromophores with the decline in pH.

Bioavailability of polycyclic aromatic hydrocarbons in Santos Bay (Brazil) and its adjacent continental shelf

Bioavailability of polycyclic aromatic hydrocarbons in Santos Bay (Brazil) and its adjacent continental shelf

Chemical properties of soil determine the persistence and bioavailability of polycyclic aromatic hydrocarbons in sewage sludge- or sewage sludge/biomass-derived biochar-amended soils

In this study the persistence (organic solvent extractable) and bioavailability (freely dissolved) of polycyclic aromatic hydrocarbons (PAHs) in soils with various properties amended with sewage sludge (BCSSL)- or sewage sludge/biomass (BCSSLW)-derived biochars was examined. Biochars produced at 600 °C were applied to soils (acidic, neutral, or alkaline) at a dose of 2% and subsequently incubated for 180 days. Here, the use of biochars regarding the soil's type was examined for the first time. Depending on the soil pH and the feedstock, the content of sum of 16 organic solvent extractable PAHs was found to decrease from 7.5 to 37% (soil + BCSSL) and from 24 to 40% (soil + BCSSLW). The decrease in the content of sum of 16 freely dissolved PAHs ranged from 18 to 36% (soil + BCSSL) and from 17 to 54% (soil + BCSSLW). In acidic BCSSL-amended soil and the alkaline BCSSLW-amended soil no statistically significant differences in the content of sum of 16 freely dissolved PAHs were noted between the beginning and end of the study. BCSSLW was characterized by a greater reduction content of organic solvent extractable PAHs in the acidic and alkaline soils, while in the neutral one – BCSSL. In turn, a larger reduction in freely dissolved PAH content in the acidic and neutral soils could be seen in the presence of BCSSLW, whereas in the alkaline soil in the presence of BCSSL. The persistence and bioavailability of PAHs in the biochar-amended soils were closely related to the chemical properties of these soils. This was confirmed by numerous statistically significant (P ≤ 0.05) relationships between organic solvent extractable PAHs and pH, cation exchange capacity, available magnesium, potassium and phosphorus, and dissolved organic carbon as well as between freely dissolved PAH and pH, dissolved organic carbon, available potassium and phosphorus content, and electrical conductivity.

Sedimentary PAH and oxidative stress biomarkers responses on Namalycastis abiuma (Polychaeta: Nereididae) from an urbanized Amazon estuary

Contamination by polycyclic aromatic hydrocarbons (PAH) in sediments and oxidative stress biomarkers responses (glutathione-S-transferase activity—GST and lipoperoxidation—LPO) on the polychaetes Namalycastis abiuma were screened along the urbanized margin of the Guajará Estuary, Brazilian Amazon coast, during dry and rainy seasons. Total 16 priority PAH concentrations ranged from 17 to 386 ng g−1 dry sediment, with higher values during the dry season. High molecular weight PAHs predominated during dry season and were probably originated from fossil fuel burning. Increased naphthalene and anthracene concentrations were noted when the maximum river flow was recorded and suggest diffuse sources from drainage of contaminated surfaces. Ecotoxicological PAH risks were low according to international sediment quality indices. Nevertheless, PAH toxicity equivalency was around 10-fold higher nearer the oil terminal than alongside the estuary. Highest GST activities at the oil terminal and industrial sites coincided with the rainy season, and combined with hydrochemical and sedimentary conditions thought to promote PAH bioavailability and a prolonged toxicant exposure. LPO approached similar levels in both seasons, suggesting that enzymatic activities were sufficient to uphold the prooxidants exposure. This result indicates that the overall estuarine condition exerts subtle oxidative stress on a keystone species and matches the low PAH ecotoxicological risks. Depositional margins within the mangrove areas and port operation are susceptible to an enhanced PAH accumulation and need special surveillance.

In-situ co-remediation of PAHs contaminated agricultural soil using blood meal and celery: An agricultural greenhouse field study

ABSTRACT Polycyclic aromatic hydrocarbon (PAH) contaminated agricultural soil is widespread globally. To develop a cost-effective remediation technique to effectively degrade PAH contaminated agricultural soil without disturbing crop production, an in-situ co-remediation of PAH contaminated agricultural soil using blood meal and celery was assessed in an agricultural greenhouse. Results showed PAH dissipation rates increased significantly in agricultural soil when co-remediated by blood meal and celery. Planting celery and addition of 5 g•kg−1 blood meal removed 53.13% of PAHs within three months. Residual PAH concentrations in plant tissue were much lower than China Standard food limits. Results indicated the ability of celery to enhance bioavailability of PAHs, and create favorable conditions for microbial, rather than direct plant uptake, played a vital role in degradation of PAHs. Addition of blood meal significantly enhanced soil enzyme activity and PAH degradation, and increased PAH remediation rate with optimal addition of blood meal (5 g•kg−1). Celery enhanced bioavailability of PAHs. Blood meal increased soil enzyme activity and increased PAH degrading bacterial activity, which acted as the main remediation pathway to co-remediate PAHs, where celery was safe to eat. Therefore, a novel in-situ agricultural soil PAH remedial method, which did not disturb normal agricultural production during remediation is presented in this study.

Chemotaxis along local chemical gradients enhanced bacteria dispersion and PAH bioavailability in a heterogenous porous medium

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous, EPA-designated priority pollutants for soil and groundwater, remaining recalcitrant to bioremediation because of limited bioavailability. In this work, we used naphthalene as a model PAH and soil bacteria Pseudomonas putida G7 to investigate the potential role of chemotaxis to enhance access to PAHs in heterogenous porous media. To this aim, we conducted transport experiments and numerical simulations with chemotactic bacteria and naphthalene trapped within a non-aqueous phase liquid (NAPL) mainly in low permeable areas of a dual-permeability microfluidic device. Microscopic imaging showed higher accumulations of chemotactic bacteria, about eight times that of nonchemotactic bacteria, at the junctures between high and low permeability regions. Pore-scale simulations for fluid flow and naphthalene revealed that the junctures are stagnant areas of fluid flow, which generated strong and temporally persistent naphthalene gradients. The landscape and densities of bacterial accumulation at the junctures were strongly regulated by flow profiles and naphthalene gradients especially those transverse to flow. We conducted macroscale simulations using convective dispersion equations with an added chemotactic velocity to account for directed migration toward naphthalene. Simulated results showed good consistency with experiments and pore-scale simulation as normalized bacterial accumulation per mm of NAPL was 7.80, 7.84 and 7.71 mm−1 for experiments, pore-scale and macroscale simulations, respectively. Macroscale simulations indicated that in the absence of grain-boundary restrictions associated with the pore structure bacterial dispersion needed to be increased by 50 % to account for the interplay between chemotactic response and naphthalene gradients at the pore-scale level. Our work details the mechanism of pore-scale chemotaxis in enhancing bioavailability of PAHs and its impact on biomass retention at the system level, which provides a potential solution toward more efficient bioremediation for contaminants such as PAHs with limited bioavailability.

Summary of the role of pyocyanin in the transformation and biodegradation of Polycyclic Aromatic Hydrocarbons

Pyocyanin is an active redox phenazine of intense blue color and specific to Pseudomonas aeruginosa. The synthesis of the molecule confers different benefits to the bacterium. Pyocyanin can control its growth and persistence in environments with high nutritional pressures, forming biofilms. As well, synthesis of pyocyanin enables P. aeruginosa tolerate and uptake highly toxic compounds such as polycyclic aromatic hydrocarbons (PAHs), considered the most dangerous compounds among all molecules found in crude oil and petroderivatives. Additionally, pyocyanin increases the bioavailability of PAHs and its metabolites are used to synthetize crucial molecules for the biodegradation of other PAHs. On the other hand, oil hydrocarbons can serve as oxygen vectors during the synthesis of pyocyanin, contributing to the sustainability of the biodegradation process. This review is a compilation of recent advances reported in the literature about the relationship between pyocyanin expression and the hydrocarbonoclastic activity of P. aeruginosa. This characteristic, for the pyocyanin-deficient strains, is important for the degradation of PAHs, a topic that has been unevenly studied.

Effect of carrier gas during pyrolysis on the persistence and bioavailability of polycyclic aromatic hydrocarbons in biochar-amended soil

AbstractIn this study the persistence (based on extractable, Ctot) and bioavailability (based on freely dissolved content, Cfree) of polycyclic aromatic hydrocarbons (PAHs) in biochar-amended soil was investigated. Biochar produced at 500 or 700 °C from sewage sludge (BC) or sewage sludge and willow (W) mixture (BCW) in an atmosphere of nitrogen (N2) or carbon dioxide (CO2) was evaluated. The biochars were applied to the real soil (podzolic loamy sand) at a dose of 2% (w/w). The content of Ctot and Cfree PAHs was monitored for 180 days. The biochar production conditions determined the Ctot and Cfree PAHs in the soil. A change of carrier gas from N2 to CO2 caused an increase in Ctot PAH losses in the soil from 19 to 75% for the biochar produced from SL and from 49 to 206% for the co-pyrolyzed biochar. As regards Cfree PAHs, the change from N2 to CO2 increased the losses of Cfree PAHs only for the biochar derived from SL at a temperature of 500 °C (by 21%). In the soil with the other biochars (produced at 700 °C from SL as well as at 500 and 700 °C from SL/W), the Cfree increased from 17 to 26% compared to the same biochars produced in an atmosphere of N2.

Long-term physical and chemical aging of biochar affected the amount and bioavailability of PAHs and their derivatives

Biochar applied into the soil is recommended as an effective tool for increasing its properties and crop productivity. However, biochar can contain some potentially toxic compounds such as polycyclic aromatic hydrocarbons (PAHs). Moreover, during biochar production or environmental application (e.g. as soil fertilizer), more toxic PAHs derivatives containing nitrogen, oxygen or sulfur can be formed. There is a lack of information on how the environmental factors affect the bioavailability of such compounds during the long-term application of BC into the soil. In the presented studies the effects of physical (freeze-thaw cycles) and chemical aging (temperatures 60 °C and 90 °C) on the total and bioavailable content of PAHs and their derivatives were estimated. The results indicate that long-term (6 months) aging affected the physicochemical characteristic of biochars promoting the formation of new C and O-containing species on the BC surface increasing their polarity and hydrophilicity. Physical and chemical aging promoted the formation of compounds with higher molecular weight and a significant (up to 550 %) increase in the bioavailability of PAHs and their derivatives. The results of this study highlight the importance of the bioavailable fraction of PAHs and their derivatives for evaluation of the toxicity of aged biochar.

Modelling polycyclic aromatic hydrocarbon bioavailability in historically contaminated soils with six in-vitro chemical extractions and three earthworm ecotypes

Accurate prediction of organic contaminant bioavailability for risk assessment in ecological applications is hindered by limited validation on relevant bioassay species. Here, six in-vitro chemical extraction methods (butanol, non-buffered and buffered hydroxypropyl-β-cyclodextrin (HPCD, Buf-HPCD), Tenax, potassium persulfate oxidation, polyoxymethylene solid phase extraction (POM)) were tested for PAH bioaccumulation prediction in three earthworm ecotypes with dissimilar exposures, Amynthas sp., Eisenia fetida, and Lumbricus terrestris, in historically contaminated soils from manufactured gas plant (MGP) sites. Extractions were compared directly and modelled in a calculation approach using equilibrium partitioning theory (EqPT) with a novel combination of different organic carbon/octanol-water partitioning parameters (KOC and KOW). In the direct comparison approach Buf-HPCD showed the closest prediction of accumulation for burrowing Amynthas sp. and L. terrestris (within 1.5 and 3.1, respectively), but Tenax and POM showed the closest approximation for E. fetida (within 1.1 and 0.9, respectively). The optimum method for predicting PAH bioaccumulation in the calculation approach depended on earthworm species and the partitioning parameters used in equations of the four models, but overall POM, which was independent of KOC, showed the closest approximation of accumulation, within a factor of 2.5 across all species. This work effectively identifies the optimum in-vitro based approaches for PAH bioavailability prediction in earthworms as a model soil health indicator for ecological risk assessment within regulatory and remediation decision frameworks.

Low bioavailability of derivatives of polycyclic aromatic hydrocarbons in biochar obtained from different feedstock

In the last years, there is great progress in the field of studies on the thermal transformation of wastes into valuable materials such as biochar. High-temperature processes, however, are connected with the formation of polycyclic aromatic hydrocarbons (PAHs) with confirmed toxicity. However, during pyrolysis, some derivatives containing oxygen, nitrogen, or sulfur can also be formed. Their toxicity is expected to be higher than parent PAHs. However, the key parameter in the agricultural application of carbonaceous materials is PAHs’ bioavailability. The aim of the presented studies was the determination of the effect of various feedstock (wheat straw (Triticum L.), willow (Salix viminalis), sunflower, residues from softwood and hardwood, sewage sludges, and residues from biogas production) on the formation of PAHs and their derivatives (O-, N-PAHs) in biochar and their bioavailability. The results indicated that the content of total and bioavailable PAHs in obtained biochar was rather low. The concentration of total PAHs in plant-derived biochar reached 57 ± 3 ng g−1 - 181 ± 8 ng g−1, whereas sewage sludge-derived biochar contained from 121 ± 6 ng g−1 to 188 ± 9 ng g−1 of PAHs. The highest concentration of PAHs was noted in biochar obtained from residues from biochar production – up to 202 ± 9 ng g−1. The total concentration of bioavailable PAHs was lower and reached 2–4.45 ng L−1 for plant-derived biochar, 3–40 ng L−1 for sewage sludge-derived biochar. The highest content of bioavailable PAHs was noted in biochar obtained from residues from biogas production: 9–42 ng L−1 indicating that increased attention should be paid to using this type of biochar. Among PAHs derivatives, nitronaphthalene, 1-methyl-5-nitronaphthalene, 1-methyl-6-nitronaphthalene, 9,10-anthracenedione, 4H-cyclopenta(def)phenanthrene, nitropyrene were determined at various levels and their concentrations were from below the limit of detection (LOD) to 28 ng L−1 for plant-derived biochar, 3–16 ng L−1 for biochar obtained from residues from biogas production, and 5–45 ng L−1 for sewage sludge-derived biochar. The content of bioavailable PAHs derivatives was, generally, one order of magnitude lower than parent PAHs derivatives, and reached from below LOD up to almost 1 ng L−1 for plant-derived biochar, from 0.5 to 2 ng L−1 for biochar obtained from residues from biogas production, and from 0.2 to almost 5 ng L−1 for sewage sludge-derived biochar confirming the safety of agricultural usage of biochar.

Characterization of Different Molecular Size Fractions of Glomalin-Related Soil Protein From Forest Soil and Their Interaction With Phenanthrene.

As a natural organic compound secreted by arbuscular mycorrhizal fungi (AMF), glomalin-related soil protein (GRSP) is an important part in soil, affecting the bioavailability of polycyclic aromatic hydrocarbons (PAHs) in it. Previous research have demonstrated that GRSP could enhance the availability of PAHs in the soil and favor their accumulation in plant roots. However, a scarcity of research exists on the different molecular weights of GRSP interacting with PAHs due to their complexation and heterogeneity. In this research, the extracted GRSP in soil was divided into three molecular weight (Mw) fractions of GRSP (<3,000, 3,000–10,000, and >10,000 Da), whose characteristics and binding capacity of PAHs were conducted by using UV–visible absorption, quenching fluorometry and, Fourier transform infrared spectroscopy. The results showed that the GRSP was composed of abundant compounds, it has a wide distribution of molecular weight, and the >10,000 Da Mw fraction was dominant. For three Mw fractions of GRSP, they have some difference in spectral features, for example, the >10,000 Da fraction showed higher dissolved organic carbon (DOC) contents, more phenolic hydroxyl groups, and stronger UV adsorption capacity than the low and middle Mw fractions. In addition, the interaction between GRSP and phenanthrene is related to the characteristics of the Mw fractions, especially the phenolic hydroxyl group, which has a significantly positive correlation with a binding coefficient of KA (k = 0.992, p < 0.01). Simultaneously, hydrophobic, NH-π, and H-bound also played roles in the complexation of phenanthrene with GRSP. These findings suggested that different GRSPMw fractions could influence the fate, availability, and toxicity of PAHs in soil by their interaction.

Drinking water treatment residue recycled to synchronously control the pollution of polycyclic aromatic hydrocarbons and phosphorus in sediment from aquatic ecosystems

Great efforts have long been made to control sediment pollution from persistent organic pollutants and phosphorus for aquatic ecosystem restoration. This study proposed a novel recycling of drinking water treatment residue (DWTR) to synchronously control sediment polycyclic aromatic hydrocarbons (PAHs) and phosphorus pollution based on a 350-day incubation test. The results suggested that DWTR addition reduced approximately 88%− 96% of potential bioavailable PAHs and 76% of mobile phosphorus in sediment. The dominant mechanisms for both reductions by DWTR were immobilization, mainly through increasing sediment amorphous aluminum and iron. The tendency of enhanced PAHs degradation by DWTR was also observed, especially for high molecular weight PAHs (e.g., chrysene, indeno(1, 2, 3-cd)pyrene, and benzo(g, hi)perylene), which decreased by approximately 21.1%− 22.0% of the total. Additionally, accompanying a clear increase in the connections of microbial cooccurrence networks, the variations in bioavailable PAHs, amorphous aluminum and iron, and other properties (e.g., pH, nitrogen, and organic matter) significantly (p < 0.01) enhanced Flavobacterium enrichment, although the enrichment of many other microbes potentially related to PAHs degradation (e.g., C1-B045) decreased after DWTR addition. Therefore, DWTR could promote the construction of a “PAHs immobilization with microbial augmentation” system while immobilizing phosphorus in sediment, indicating the high feasibility of controlling multiple sediment pollution.

Microbial communication during bioremediation of polyaromatic hydrocarbons

Human activity pollution has been shown to harm the environment, ecology, and health impacts. The polycyclic aromatic hydrocarbons (PAHs) produced by the industries such as tannery, distillery, pulp paper, and oil refineries are a major source of contaminant. PAHs are found all across the world, owing to long-term human pollution sources. PAHs' physico-chemical features, such as hydrophobicity and electrochemical stability, contribute to their environmental persistence and contribute to their carcinogenic and health effects. Numerous analytical and biological techniques for the qualitative and quantitative assessment of PAHs have been proposed. Bioaccumulation, adsorption, chemical oxidation, photolysis, volatilization, and microbiological degradation are the principal breakdown pathways of PAHs in the environment. Microbial populations, such as bacteria, fungi, and algae, play a crucial role in the biological elimination of PAHs. Oxidase, manganese peroxidases, lipases, and laccases are the enzymes involved in PAHs breakdown. The synthesis of surfactants by bacteria increases PAHs bioavailability and improves the elimination process of PAHs. Temperature, pH, aeration, moisture content, nutrition availability, absence of hazardous chemicals, and the kind and number of degrading microbial populations are all factors that influence PAHs decomposition. Microbial degradation mechanisms result in intermediate metabolites and carbon dioxide mineralization. The elimination of PAHs is improved by molecular approaches such as gene engineering and protein engineering. This review discussed the benefits of bioremediation strategies that were investigated for precise evaluation and were trusted at both the regulatory and scientific studies levels.

Differential accumulation of polycyclic aromatic hydrocarbons (PAHs) in three earthworm ecotypes: Implications for exposure assessment on historically contaminated soils

This study compared accumulation of the 16 US-EPA priority polycyclic aromatic hydrocarbons (PAHs) in three different earthworm ecotypes, Amynthas sp., Eisenia fetida, and Lumbricus terrestris, in four historically (> 50 years) contaminated manufactured gas plant (MGP) soils using bioassays. Epi-endogeic deep burrowing and soil ingesting Amynthas sp. accumulated significantly more ∑16 PAHs than any other species (upto 8.7 times more), and epigeic surface dwelling E. fetida showed the lowest ∑16 PAH accumulation. Results indicated the importance of earthworm habit and physiology on PAH partitioning into earthworm lipids. Exposure to soil borne PAHs via the gut, as compared with passive diffusion from pore water, was important in species tested, being most evident in burrowing species Amynthas sp. and L. terrestris and for the desorption-resistant higher molecular weight (HMW) PAHs. Biota-soil accumulation factors (BSAF) were low, as influenced by aging, sequestration and strong PAH sorption to secondary sorptive phases in the historically contaminated soils. Bioconcentration factors (BCFs) calculated from freely dissolved pore water PAH concentrations derived from polyoxymethylene solid-phase extractions (POM) were species specific, indicating stronger relationships with octanol-water partition coefficient (KOW) for Amynthas sp. and L. terrestris than for E. fetida. Modelling demonstrated that KOW values were not a reliable proxy for BCF in equilibrium partitioning theory (EqPT) to predict bioavailability for the range of earthworms tested, being less accurate for E. fetida compared to the burrowing species. The study showed that including burrowing and soil feeding earthworm species, such as Amynthas sp. and L. terrestris, in standard testing would benefit regulatory decisions for more accurate quantification of PAH bioavailability in ecological risk assessment on historically contaminated soils.

The antioxidant defense responses of Hordeum vulgare L. to polycyclic aromatic hydrocarbons and their derivatives in biochar-amended soil

The recent studies indicated that the biochar (BC) may be a source of polycyclic aromatic hydrocarbons (PAHs) as well as their oxygen, nitrogen, or sulfur-containing derivatives that are considered as more toxic pollutants than their parent compounds. Here, the assessment of the impact of various biochars addition (1% wt.) to soil on barley Hordeum vulgare L. growth was presented. The concentrations of bioavailable PAHs and their derivatives in biochar were determined. PAHs increased reactive oxygen species generation resulting in oxidative stress in organisms. In this study, the response of soil-grown plants was examined in terms of the activity of the antioxidative enzymes (superoxide dismutase, catalase, peroxidase), lipid peroxidation, and the expression of genes related to oxidative stress. The results indicate that despite low content of a bioavailable fraction of parent compounds and their derivatives (up to 4.45 ± 0.24 ng gbiochar−1 and 0.83 ± 0.03 ng L−1, respectively) the biochemical response of plant was present, the activity of superoxide dismutase increased up to 2 times, but the activity of the other enzymes was lowered. The transcript level values support the studies on enzymatic activity. The presence of PAHs and their derivatives induced oxidative stress slightly but the plant was able to mitigate it.

Oral bioavailability reveals an overestimation of the toxicity of polycyclic aromatic hydrocarbons in atmospheric particulate matter

Polycyclic aromatic hydrocarbons (PAHs) in atmospheric particulate matter have adverse effects on human health, yet total PAH concentrations should overestimate the toxicity compared to the bioavailable amount of PAHs. To explore this hypothesis, we measured PAHs oral bioavailability in vitro in particulate matter with aerodynamic diameter lower than 10 µm (PM10) using a test that mimics the human digestive system. This assay combines the use of simulated gastrointestinal fluids and a dialysis membrane to simulate intestinal absorption. Results show that oral PAH bioavailability was below 5%, with fluorene, anthracene, acenaphthene and phenanthrene as the most bioavailable PAHs. Data suggest no carcinogenic risk of oral bioavailable PM10-bound PAHs following a health risk assessment via inhalation-ingestion by using benzo(a)pyrene-equivalent carcinogenic concentration and hazard indexes. To our best knowledge, this is the first research study of in vitro oral bioavailability estimation of PM10-associated PAHs.

Comparing the sorption of pyrene and its derivatives onto polystyrene microplastics: Insights from experimental and computational studies

In this study, the sorption behaviors and mechanisms between polystyrene microplastics (micro-PS) and 4-rings polycyclic aromatic hydrocarbons (PAHs) pyrene (Pyr) and its derivatives (S-Pyr), including 1-methylpyrene (P-CH3), 1-hydroxypyrene (P-OH), 1-aminopyrene (P-NH2), 1-pyrenecarboxylic acid (P-COOH) were investigated at neutrality. The results revealed that the sorption rates of micro-PS for S-Pyr were higher than those for parent Pyr. Meanwhile, -CH3 could slightly facilitate the sorption, whereas -OH, P-NH2, and P-COOH intensively inhibit the sorption of S-Pyr onto micro-PS. The sorption capacities of Pyr/S-Pyr increased with decreasing size of micro-PS. Besides, the effects of salinity and temperature on the sorption characteristics of micro-PS for Pyr/S-Pyr depended on their substituents. Combined with experimental and computational methods, it could be concluded that the main sorption mechanisms were possibly hydrophobic interaction, π-π interaction and pore-filling. The observations reported here could improve predictions of environmental behaviors and bioavailability of PAHs and micro-PS.